Review Article RecentAdvancesinQuartzCrystalMicrobalance...

Hindawi Publishing CorporationJournal of SensorsVolume 2011, Article ID 571405, 13 pagesdoi:10.1155/2011/571405

Review Article

Recent Advances in Quartz Crystal Microbalance-Based Sensors

Sandeep Kumar Vashist1, 2 and Priya Vashist1

1 Centre for Bioanalytical Sciences, National Centre for Sensor Research, Dublin City University, Glasnevin, Dublin 9, Ireland2 NUSNNI-NanoCore, T-Lab Level 11, National University of Singapore, 5A Engineering Drive 1, Singapore 117580

Correspondence should be addressed to Sandeep Kumar Vashist, [email protected]

Received 14 May 2011; Accepted 30 June 2011

Academic Editor: Michele Penza

Copyright © 2011 S. K. Vashist and P. Vashist. This is an open access article distributed under the Creative Commons AttributionLicense, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properlycited.

Quartz crystal microbalance (QCM) has gained exceptional importance in the fields of (bio)sensors, material science,environmental monitoring, and electrochemistry based on the phenomenal development in QCM-based sensing during the lasttwo decades. This review provides an overview of recent advances made in QCM-based sensors, which have been widely employedin a plethora of applications for the detection of chemicals, biomolecules and microorganisms.

1. Introduction

In 1880, Jacques and Pierre Curie discovered that when amechanical stress is applied to certain materials such asquartz, a voltage proportional to the stress is produced [1].In 1959, Sauerbrey demonstrated the dependence of quartzoscillation frequency on the change in surface mass [2]. Hecoined the term quartz crystal microbalance (QCM) in late1950’s, and it was his work that led to the use of quartz plateresonators as sensitive microbalances for thin films. Whenvoltage is applied to a quartz crystal causing it to oscillate at aspecific frequency, the change in mass on the quartz surfaceis directly related to the change in frequency of the oscillatingcrystal, as shown by the Sauerbrey equation(1)

Δm = −C · Δ f . (1)

The change in QCM frequency determines the mass ofanalyte adsorbed in ng/cm2. Sauerbrey equation is valid forelastic subjects such as metallic coatings, metal oxides, thinadsorbed layers, which don’t dissipate any energy duringoscillation. It doesn’t apply to inelastic subjects such ascells, polymers, and biomolecular systems, where there isenergy loss due to viscous damping during oscillation. It isinvalid for soft or viscoelastic films, which do not couplecompletely with the oscillating crystal, thereby, causing anunderestimation of mass. When the change in mass is greaterthan 2% of the crystal mass, the Sauerbrey equation becomes

inaccurate, that is, there is no linear relationship between Δ fand Δm. QCM with dissipation (QCM-D) was developed tomeasure the energy dissipation in biological samples.

A QCM is a shear mode device, consisting of a thin quartzdisk with coated electrodes, where the quartz crystal platemust be cut to a specific orientation with respect to thecrystal axes, that is, AT or BT cut so that the acoustic wavepropagates perpendicularly to the crystal surface. The reso-nant frequency of the quartz single crystal depends on theangles with respect to the optical axis at which the wafer wascut from the crystal. The most commonly used angle is ATcut, that is, 35◦15′ from the Z axis of the crystal. The temper-ature dependence of the resonant frequency of AT-cut crystalis essentially zero at 25◦C as they have low temperaturecoefficient at room temperature, which causes minimumchanges in frequency due to variation in temperature. Thereis decrease in the frequency of QCM due to the deposition ofmass on its surface. The mass sensitivity of QCM is depen-dent on the thickness of the crystal, which determines itsresonant frequency. The thinner is the QCM, the higher is itsresonant frequency and sensitivity. However, thinner QCMis very fragile. Most commercially used QCM crystals are0.5 inches in diameter. Optically polished crystals are recom-mended for liquid-phase QCM sensing as they have reducednonspecificity. The changes in frequency and signal attenu-ation due to changes in viscosity of liquid makes the liquid-phase QCM sensing very challenging and necessitates the useof an appropriate algorithm to separate out the effects.

2 Journal of Sensors

1950–1980 1981–1990 1991–2000 2001–present

Nu

mbe

rof

arti

cles

publ

ish

ed

0

1000

2000

3000

4000

Figure 1: Number of articles published in the last few decadespertaining to QCM-based sensors (based on data taken from http://www.sciencedirect.com/ on May 12, 2011 using “quartz crystal mic-robalance” and “sensors” in the advanced search option).

There has been a rapid increase in the number of publica-tions related to QCM sensing applications during the last fewdecades (Figure 1). QCMs have been used for multifariousapplications in various disciplines of science and technologyfor the detection of metals in vacuum, vapors, chemicalanalytes, environmental pollutants, biomolecules, diseasebiomarkers, cells, and pathogens (Table 1). They are alsoemployed for deposition rate monitoring, electrochemicaldeposition, corrosion studies, detection in gas chromatogra-phy, and controlling thickness and composition of sputteredmaterials. Presently, there are several companies that aredealing with QCM-based systems (Table 2).

The sensitivity and specificity of QCM-based immuno-sensors is dependent on the immobilization of recogni-tion layer. Various strategies have been employed for theimmobilization of antibodies on the crystal surface. Passiveadsorption of antibodies has been the most widely usedmethod. However, it leads to random immobilization ofantibodies on the surface, which may not be in functionallyactive orientation. The crystallizable fragment (Fc)-bindingproteins such as protein A, protein G- and protein A/Gare employed for oriented immobilization of antibodieson the gold-coated QCM surface such that their antigen-binding sites (Fab region) are completely free for bindingantigens. Another strategy employs the initial generationof amino groups on the QCM surface by treatment with3-aminopropyltriethoxysilane followed by the activation ofamine-functionalized surface with glutaraldehyde to gener-ate aldehyde groups, which bind to the antibody throughits amino groups. The interactions between thiols andgold are very strong and have also been exploited forantibody binding by employing self-assembled layers ofthiols and sulphides. The avidin-biotin interactions have alsobeen employed, where the avidin/streptavidin-coated QCMgold-surface is bound to the biotinylated antibody. Otherapproaches based on the use of polyelectrolytes, polymers,and Langmuir-Blodgett films have also been used.

Presently, several advanced analytical techniques suchas fourier transform infrared (FTIR) spectrometry, gaschromatography (GC), and mass spectrometry (MS) areused for the accurate detection of various chemicals. Butthey are time consuming, need expensive instrumentation,and can only perform offline analysis. QCM provides oneof the most promising sensor technology based on its lowcost, rapid response, portability, nonhazardous label-freereal-time procedure, and high sensitivity, which is ideal forthe sensitive online detection of analytes and holds a greatpromise for the next-generation sensors.

2. Detection of Chemicals

2.1. Volatile Organic Compounds. The detection of volatileorganic compounds (VOCs), that is, alcohols, ethers, esters,NO2, ammonia, halocarbons, chemical warfare agents, toxicgases, and so forth, is the main element of sensor technologyworldwide based on the increasing threat of terrorist attacksand continuous online monitoring of military storage sta-tions.

QCM-based multianalyte detection system, composedof six chips sensor module coated with synthetic polypep-tides together with conducting polymers, was developedfor the detection of acetic acid, butyric acid, ammonia,dimethyl amine, benzene, chlorobenzene, and their mixtures[3]. It demonstrated sensitive and selective detection, anddiscrimination via characterized odor profiles of all testedVOCs in various sensing applications. The use of principalcomponent analysis (PCA) led to additional exploration ofthe sensor module properties as simple pattern recognitiontechnique was followed.

Alcohols are volatile organic solvents being used in medi-cine, laboratories, industries, and many workplaces. Pro-longed exposure to methanol vapour for a long time causessome diseases. QCM-based technique, based on the deposi-tion of a thin film of polyaniline (PANI) salt, was employedfor the detection of various primary aliphatic alcohols suchas ethanol, methanol, 1-propanol, and 2-propanol vapours[4]. PANI was used as the sensing material due to its highenvironmental stability, good performance at room tempera-ture, high electrical conductivity, good reversibility, and goodreproducibility. The vapours adsorbed into the thin film-coated QCM led to increase in its frequency shifts due to thehydrophilic nature of film, electrostatic interactions, andtype of alcohol. The biosensor signal, that is, the frequencyshift, had a linear correlation with the concentration ofprimary aliphatic alcohol vapours in the range of 2–17 mg/L. The sensor demonstrated good reproducibility andreversibility.

QCM-based ethanol sensor was developed which showedpromising results for the online monitoring of ethanol, 0.26–0.70% (w/w) in whole meal bread and 0.68–2.06% (w/w)in durum-wheat bread [5]. The limit of detection and thelimit of quantitation for ethanol were 1.73 × 10−2 μg and3.69 × 10−2 μg, respectively. It can be used as a qualitycontrol during bakery production for the online monitoringof ethanol concentration.

Journal of Sensors 3

Table 1: Companies dealing with QCM systems.

Companies Websites

Q-Sense http://www.q-sense.com/

Elchema http://www.elchema.com/EQCN.htm

Inficon http://www.inficonthinfilmdeposition.com/en/index.html

Masscal http://www.masscal.com

ElbaTech Srl http://www.elbatech.com/

Resonant Probes http://www.resonant-probes.de/index.htm

KSV —

Institute of Physical Chemistry, Polish Academy of Sciences http://www.ichf.edu.pl/offers/of en/aparat.html

Tectra GmbH http://www.tectra-gmbh.com/qmb.htm

Stanford Research Systems, Inc. http://www.thinksrs.com/products/QCM200.htm#

International Crystal Manufacturing Co, Inc http://www.icmfg.com/qcm crystals.html

QCM Research http://www.qcmresearch.com/home.html

QCM Labs http://www.qcmlab.com/index.htm

CH Instruments, Inc http://www.chinstruments.com/Products.html

Lap-Tech http://www.laptech.com/

Sierra Sensors http://www.sierrasensors.com/

Eco Chemie http://www.ecochemie.nl/?pag=13/#EQCM

QCM-based sensor, with high sensitivity and quickresponse, was developed for the detection of methyl mer-captan (CH3SH) by increasing the surface area of sensingpolymeric film [6]. Poly(ethylene imine) (PEI) was used aspolymeric layer, whereas Al2O3 porous film was used toincrease the surface area by coating it using sol-gel methodon the QCM substrate between the QCM electrode andpolymeric film. The developed sensor detected 100 ppb ofCH3SH gas and had interference with moisture, which canbe corrected by using humidity sensor as feedback source.

QCM sensor array, with high sensitivity and specificity,was demonstrated for the detection of four gaseous chemicalagents, that is, dimethyl methylphosphonate (DMMP), N,N-dimethylacetamide (DMA), 1,5-dichloropentane (DCP),and dichloroethane (DCE) [7]. Four appropriate coatingmaterials were selected from 15 coating materials by applyingPCA with hierarchical cluster methods to the sensor responsedata set collected from 15 QCM sensors for 12 analytes.These four coating materials were used to coat four QCMs ina sensor array, and PCA was adapted to classify four simulantgases.

Poly(vinylidene fluoride) (PVDF)-coated QCM sensorwas developed for the detection of dimethyl methylphos-phonate (DMMP) vapours, a stimulant of nerve agents [8].The frequency shifts versus DMMP concentrations in therange of 5–60 ppm exhibit a perfect linear correlation witha correlation coefficient of above 0.997. The sensitivity toDMMP vapour was almost identical in various humiditycircumstances but higher in a lower temperature range.

Calixarene film-coated QCM sensors were used for thedetection of volatile organic compounds (VOCs), that is, aro-matics, chlororganics, ketones, and alcohols [9]. Calixarenesform host-guest complexes, where calixarene molecule actsas host while metal ions and different organic compoundsact as guests. The sensitivity and selectivity of calixarenes

vary depending on the numbers of aryl fragments and thebinding of different functional groups to upper and lowerrims. The numbers of aryl fragments affect the size and shapeof the cavity. Phosphorous-containing calixarenes showedmaximal sensitivity, which makes them attractive for sensorapplications. Further efforts are devoted to enhance thesensitivity and selectivity of sensor coatings for the detectionof specific analytes.

QCM-based VOC vapour sensor was developed for thedetection of toluene and p-xylene [10]. Toluene and p-xylenemolecular imprinted polymers (MIPs), composed of methylmethacrylate (MMA) as a monomer and divinylbenzene(DVB) as a cross-linking agent, were prepared in the presenceof toluene and p-xylene using conventional cross-linkingpolymerization. These solvent molecules produced theirown recognition sites inside the polymer matrix duringthe polymerization process. MIP powders were blendedwith PMMA and coated on QCM for the development ofVOC sensor. The toluene and p-xylene imprinted polymersshowed their specific tendencies to reversibly bind tolueneand p-xylene preferably based on the molecular imprintingeffect although the response time was slow due to thepresence of matrix polymer around the MIP particles. Thus,there is tremendous potential in this technique for thedevelopment of QCM-based sensors for VOCs. However,further improvements are still desired for increasing theselectivity and response time.

Miniaturized QCM arrays, with up to 36 QCM on asingle AT-cut quartz blank, were developed and used forthe detection of toluene in water by coating the QCMsensor array with different layers such as polystyrene, amyl-calix[8]arene, and β-cyclodextrin [11]. The sensitivity ofthe polystyrene coating to the toluene in water was directlyproportional to the resonant frequency. However, the higheris the sensitivity, the higher is the noise due to lower quality


Table 2: QCM-based sensing applications.

Analytes Detection limits References

Acetic acid, butyric acid, ammonia, dimethyl amine, benzene, andchlorobenzene

N.M.∗ [3]

Primary aliphatic alcohols such as ethanol, methanol, 1-propanol,and 2-propanol

2–17 mg/L [4]

Ethanol 1.73 × 10−2 μg [5]

CH3SH 100 ppb [6]

DMMP, DMA, DCP, DCE N.M.∗ [7]

DMMP 5–60 ppm [8]

VOCs such as aromatics, chlororganics, ketones, and alcohols N.M.∗ [9]

Toluene and p-xylene N.M.∗ [10]

Toluene N.M.∗ [11]

Xylene isomers 0–200 ppm [12]

Alcohols, esters, acids, and aldehydes N.M.∗ [13]

Bisphenol-A 0.01 ng/mL [14]

TCDD 0.1–100 ng/mL [15]

DDVP 6.5–32.5 ppm [16]

1-NAP and 2-NAP8.362 × 10−7 mol/L for 1-NAP2.146 × 10−7 mol/L for 2-NAP

[17]

HCl ppt level with sensitivity of 0.1 ppm/Hz [18]

250 ppb/Hz sensitivity [19]

Methane 0.05% (v/v) [20]

N.M.∗ [21]

NO 25 ppb/Hz sensitivity [22]

NO2Sub-ppm level with sensitivity of 1200 Hz/h for

50 ppm NO2[23]

Chloroform N.M.∗ [24]

N.M.∗ [25]

NH3 N.M.∗ [26]

0.3–15 ppm with LOD of 0.1 ppm [27]

HCHO 3 ppm [28]

L-mandelic acid N.M.∗ [29]

Orange and melon flavors N.M.∗ [30]

Ethanol, acetone, and trichloroethylene gas mixtures N.M.∗ [31]

Humidity Sensitivity of 12.32 Hz/RH% [32]

Ag ions N.M.∗ [33]

Olive oils N.M.∗ [34]

Nanoparticles (Si and Ag nanopowder, rhodamine B, and ferrocene) Linear up to 1300 μg/mL [35]

Glucose 0.01–7.5 mM with LOD of 5 μM [36]

Albumin 60–150 ppm [37]

PSA and PSA-ACTLinear dynamic range up to 150 ng/mL with

LOD of 0.29 ng/mL[38]

CRP N.M.∗ [39]

EPGF 0.01–10 μg/mL [40]

L tryptophan LOD 8.8 μM [41]

Glycoproteins 50 μg/mL–1 mg/mL [42]

Folic acidLinear range of 0–100 μM with LOD of

15.4 μM[43]

Vibrio harveyi 103–107 CFU/mL [44]

Campylobacter jejuni N.M.∗ [45]

D. desulotomaculum 1.8 × 104–1.8 × 107 cfu/mL [46]∗

N.M.: Not mentioned.


factor. Therefore, the toluene detection has to be done at theoptimum resonant frequency, which depends on the stabilityof temperature and pressure control.

QCM sensor array having four QCMs was employed forthe detection of xylene isomers in the range of 0–200 ppmwith an accuracy of about 1% [12]. The sensor was specificfor m-xylene and p-xylene without any cross-sensitivity withthe residual water, thereby enabling analyte detection in thepresence of variable ambient humidity. The supramolecularhost molecules were used as coating materials for QCMresonators and combined with multivariate data analysisfor the detection of xylene isomers. The low-cost sensorarray is highly stable chemically and physically, and thusappropriate for specific continuous online monitoring ofgaseous analytes under very harsh conditions.

PEGylated lipopolymer containing disulphide as sup-ports for the lipid and lipopolymer odor sensing materialswas chemisorbed on QCMs [13]. The sensors with supportswere found to be more sensitive than the nonsupportedcounterparts due to higher fluidity of supported films. Thiswas evident by the evaluation of the overall sensing proper-ties by PCA. The sensors were able to discriminate among theten odorants tested, that is, alcohols (1-butanol, 1-hexanol,trans-2-hexenol), esters (butyl acetate, hexyl acetate, trans-2-hexenyl acetate), acids (isobutyric, hexanoic), and aldehydes(butanal, trans-2-hexenal).

2.2. Bisphenol-A, Dioxin Compounds, DDVP, and Naphthol.Bisphenol-A (BPA)/[4,4′-(1-methylethylidene) bisphenol]was detected using anti-BPA monoclonal-antibody immo-bilised on QCM [14]. After the specific detection of BPA,the signal was enhanced by adding a secondary antibodytagged with a conjugated microsphere. Anti-BPA anti-body was conjugated to 2-methacryloyloxyethyl phospho-rylcholine (MPC) polymeric nanoparticles, and polystyrenenanoparticles of the same size, that is, 202 nm. MPCpolymeric nanoparticles tagged anti-BPA had greater signalenhancement with highly stable signal as MPC polymericnanoparticles had excellent colloidal stability resulting fromstrongly solvation with water molecules that resisted thecoagulation of these nanoparticles. The signal enhancementstep decreased the limit of detection from 0.1 ng/mL to0.01 ng/mL, thereby, demonstrating the increase in analyticalsensitivity of assays dealing with small analytes.

In another approach [47], MIP was bound to the self-assembled monolayer (SAM)-coated QCM Au electrode forthe detection of BPA. SAM, composed of 2-aminoethane-thiol and 11-mercaptoundecanoic acid, had ion-pair inter-actions with the functional monomers in MIP to form pro-per adhesions. MIP contained specific cavities by self-orga-nized structure of functional monomers around a template.The sensor can detect BPA selectively in the liquid phase witha sensitivity of 100 ppb. It was observed that polymerizationsolution without solvent had better sensor performance,MIP-QCM sensor with SAM was better in terms of stabil-ity than that without SAM, greater weight of membraneimproved the sensitivity of the sensor, and the optimizedmaterial type and its composition can lead to improvedsensor.

A portable QCM-based dioxin sensor was developedto detect the concentration of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) [48], which is the most toxic moleculeamong dioxin-like compounds and is considered as a refer-ence for this class of compounds. QCM surface was chem-ically treated with cysteamine and glutaraldehyde, and thenbound to anti-TCDD monoclonal antibody. The unreactedaldehyde groups were blocked with glycine. MPC polymerwas used as a stabilizer to reduce the nonspecific bindingof the antigen solution and to stabilize the immunologicactivity of antibody-functionalised QCM. The biosensor waseffective for the analysis of dioxins in fly ash samples [15, 48].There was a linear response to 0.1–100 ng/mL TCDD withlinear correlation of 0.99, which was similar to ELISA.

QCM sensor, with enhanced sensitivity, was developedfor organophosphorous pesticide o,o-dimethyl-o-2,2-dich-lorovinyl phosphate (DDVP) by modifying the geometryand size of the electrodes and depositing conductive poly-mers on the surface of the electrode [16]. The change inresonant frequency, which is a measure of the electrical loa-ding, corresponds to the change in electrostatic capacitance.The sensor’s sensitivity was directly proportional to theconductivity of polymer coating. The capacitance was inthe range of 0.198–0.187 pF for the poly(3,4-ethylenedio-xythiophene) (PEDOT)-conductive polymer film. The rela-tionship between PEDOT-coated sensor response and DDVPconcentration was linear in the range of 6.5–32.5 ppm.PEDOT film-coated sensor was used to measure three DDVPsamples with the relative standard deviation of less than 5%.

The high sensitivity of QCM, with β-cyclodextrin (β-CD)/TiO2 composite film, was coupled with excellentpredictive ability of chemometrics, for the simultaneousdetermination of 1-naphthol (1-NAP) and 2-naphthol (2-NAP) in human urine samples [17]. β-CD was immobilizedonto the QCM surface using nanocrystalline TiO2 films assubstrates. The correlation coefficients for 1-NAP and 2-NAPwere 0.993 and 0.990, respectively, whereas the LODs were8.362× 10−7 mol L−1 and 2.146× 10−7 mol L−1, respectively.

2.3. Gaseous Analytes. QCM-based HCl gas sensor wasdeveloped using morpholine-functional poly(styrene-co-chloromethylstyrene) copolymer coatings, which was goodfor one-shot detection of HCl gas as it bind irreversibly tothe sensor coating [18]. The sensitivity of the sensor wasdependent on the chemical structure and the compositionof copolymer. It detected ppt level of HCl with sensitivity of0.1 ppm/Hz for 10 min sensor operation. The largest sensi-tivity was obtained when the sensor film coating copolymerwas composed of 40 mol% chloromethylstyrene cross-linkedwith 5 mol% divinylbenzene, and the film thickness wasgreater than 2 μm. However, substantial interference wasproduced by changes in humidity and NO2, which can biasthe use in some industrial applications such as the analysis ofcombustion gases. The device was, however, not affected byother gases such as O2, CO2, and SO2.

In another approach, QCM-based sensor was developedfor the detection of HCl gas in air-using coatings of threedifferent kinds of poly(acrylamide) derivates [19]. Thesensitivity, response time, and reversibility of the sensor were


dependent on the structure of the amide group. The polymerpoly(N,N-dimethylacrylamide) (PDMAA) was the best forHCl sensing with a sensitivity of about 250 ppb/Hz. However,the sensor still had considerably high irreversible responsetowards NO2 gas and high interference to changes in test gashumidity, which limit its practical applications. The futureefforts by the group are devoted to prepare a reliable andpractical HCl gas sensor.

Supramolecular cryptophane-A-based QCM sensor wasused for the selective and rapid detection of methane withhigh recovery at room temperature and a detection limit of0.05% (v/v) [20]. The supramolecular cryptophane-A wassynthesized from vanillyl alcohol by double trimerisationmethod and deposited on the QCM surface by electrospray-ing.

PANI/PdO composite, synthesized by in situ chemicaloxidative polymerization of aniline with PdO nanoparticles,was deposited on QCM through layer-by-layer self-assemblymethod and employed for detecting methane [21]. Thesensor response decreased with the increase in relativehumidity and was better at room temperature than at 50◦C.

QCM sensor for the detection of nitric oxide (NO) ingaseous state was developed by immobilizing cobalt phthalo-cyanine (CoPc) in a mesoporous silica matrix depositedon QCM [22]. CoPc/mesoporous silica hybrids were pre-pared by thermal calcinations process and characterisedby fourier transform infrared spectroscopy (FTIR) andscanning electron microscopy (SEM). CoPc/mesoporoussilica-coated QCM was compared with nonmodified QCMand CoPc-modified QCM for sensitivity enhancement.CoPc/mesoporous silica-coated QCM had highest sensitivityof up to 25 ppb/Hz with minimum cross-sensitivity tocarbon monoxide (CO).

Morpholine-functional cross-linked copolymer coatingswere developed for QCM for the detection of sub-ppmlevel of nitrogen dioxide in air [23]. The cross-linkedpoly(styrene-co-chloromethyl styrene) copolymer reactedwith morpholine to generate the morpholine-functionalcross-linked copolymer. The developed QCM-based sensor issuitable for one-shot detection of NO2 concentrations in air.The largest sensitivity obtained was 1200 Hz/h for 50 ppm ofNO2.

The paracyclophanes B44TOS and CP44 were coated onthe surface of QCM, and chloroform vapors were detected bythe formation of host-guest complexes between chloroformand paracyclophanes [24]. The mass-sensitive detection wasfurther confirmed by FTIR spectroscopy and Brunauer,Emmett, and Teller theory (BET) adsorption analysis.

Electrospun nanoporous membrane-coated QCM sensorwas developed for the detection of ammonia [25]. The elec-trospun nanofibers, composed of cross-linkable poly(acrylicacid) (PAA) and poly(vinyl alcohol) (PVA), and havingdiameter of 100–1400 nm, were deposited on QCM by elec-trospinning. The average diameter and rigidity of nanofibersincreased with the increase in viscosity and conductivity ofthe homogeneous blend solution of PAA and PVA due tothe increased PAA content. The sensitivity of nanofibrousmembrane-coated QCM was much higher than that ofcontinuous films-coated QCM. The sensing properties were

In Out

AU

AU

QCM

QCM

Ti(O-nBu)4 vapor

Deposition of Ti(O-nBu)4 vapor(10 min)

N2 purge andhydrolysis

PAA

PAA

in water (20 min, 25◦C)

TiO2

Repeat a

a

→c

c

Mercaptoethanol-modified(9 MHz)

b

Washing and drying

(a)

Dry airL1

MFCL2

Dilution

Samplebottle

PC

Frequencycounter

QCM chamberAnalyte

Heater

Value

(b)

Figure 2: (a) Schematic illustration of the film preparation by thegas phase surface sol-gel process. (b) Schematic diagram of theQCM measurement setup (Lee et al., 2010) [27]. (Reprinted withpermission from ACS Publications.)

affected by the content of PAA in nanofibrous membranesand relative humidity.

A highly selective, reproducible, and stable sensor, basedon ZnO nanorods-coated QCM, was developed for detectingNH3 at room temperature [26]. Vertically-aligned ZnOnanorods, with diameter of 100 nm and height of 3 μm, weresynthesized directly on the Au electrode of QCM by wetchemistry at 90◦C. The sensor showed good selectivity toNH3 over liquefied petroleum gas, N2O, CO, NO2, and CO2.

QCM sensor was developed for the sensitive detection ofamine odors by employing an ultrathin film formed by thealternate adsorption of TiO2 and polyacrylic acid (PAA) [27](Figure 2). The developed sensor was very fast in response,stable in a relative humidity range of 30–70%, and had alinear range of 0.3–15 ppm with LOD of 0.1 ppm for thedetection of ammonia, which binds to the free carboxylicgroups of PAA by acid-base interactions. The TiO2/PAA400

ultrathin film was capable of condensing 15 ppm ambientammonia concentration to ∼20,000 ppm. The sensitivityto n-butylamine and ammonia was found to be higher incomparison to pyridine due to differences in their molecularweight and basicity.


QCM

RH = 97%

Saturatedsolution

RH = 11.3%

Labview

Agilent53131A

Voltage in

out

The oscillatinggenerationcircuitSignal

Figure 3: QCM setup for humidity testing (Zhu et al., 2010) [32]. Reprinted with permission from Elsevier B.V.

Electrospun nanoporous polystyrene fibres, with highsurface area-to-volume ratio (∼47.25 m2/g), were depositedon polyethyleneimine (PEI)-functionalized QCM andemployed for highly sensitive and rapid detection of HCHOwith a LOD of 3 ppm [28]. The PS fibers, electrospun fromhigher concentration of PS solution (13 wt%), had largerpore size and greater surface area than PS fibers electrospunfrom less concentration of PS. Therefore, the sensor responseof PEI-PS (13 wt%) for the detection of 140 ppm HCHOwas four fold greater than that of PEI-PS (7 wt%).

2.4. Chiral Recognition, Odor Approximation, and Com-position Analysis. An L-phenylalanine-coated QCM sensorand vapour-diffused molecular assembly (VDMA) reactiontechnique were employed for the highly selective chiralrecognition of L-mandelic acid (L-MA) with the chiraldiscrimination factor, that is, L-MA/D-MA of about 8 [29].The developed QCM-based procedure was simple and betterthan the diastereomeric crystallization technique, where thescreening of resolving agents is challenging. The QCM-chiral recognition results were in agreement with the resultsobtained by diastereomeric crystallization separation ofracemate MA using L-phenylalanine as resolving agent. Theselective detection of L-MA was further confirmed by contactangle measurements. Similar strategy can be adopted for thescreening of suitable resolving agents for chiral enantiomersin chiral resolution.

Odor approximation is a challenging task as odorsare mixtures of hundreds of different kinds of molecules.However, there are some character impact odorants in thecase of fruit flavours, which are helpful for performingan approximation of fruit flavours. An array of QCModor sensors coated with different materials, such as lipidsand stationary phase material of gas chromatography, wasemployed for odor approximation of orange and melonflavours [30]. The lipids used were divaleroyl phosphatidylcholine (DVPC), cardiolipin (CL), and cerebrosides (CSs),whereas the stationary phase material of gas chromatogra-phy employed was apiezon-L (Ap-L). Initially, the steady-state sensor responses to single flavour components were

measured. Thereafter, the important odor components wereestimated by computational two-level quantization method.The experimental approximation was performed using thesteady-state sensor responses and PCA. The orange flavourcan be approximated using an array of four sensors, wherethe odor approximation can be done using three odorcomponents, that is, linalool, decanal, and citral. However, inthe case of melon flavour as the number of odor componentsincreased, a DVPC-coated QCM was further included as thefifth component of the sensor array. Human sensory test wasperformed to evaluate the similarities between approximatedodors and original ones, which were observed to be high inthe case of orange flavour. But it is possible to approximatethe melon flavour much better by increasing the number ofodor components in approximate flavour.

An array of eight phthalocyanine-coated QCM sensorsand an artificial neural network were used for findingthe composition of gas mixtures [31]. The preprocessingof digital data collected from the sensor responses wasdone by a sliding window algorithm followed by a three-layer artificial neural network, which was used to deter-mine the composition of the gas mixtures. The developedsensor system was tested with various gas mixtures suchas ethanol-acetone, ethanol-trichloroethylene, and acetone-trichloroethylene with a success rate of greater than 84% andoverall prediction error of 10.6%. The developed procedureis only applicable to the gaseous mixtures belonging to acertain specified categories but can be readily expanded toother gas species.

2.5. Other Applications. Mesoporous silicate SBA-15 withmonodisperse hexagonal lamelliform was prepared andcoated on QCM to form low-cost, highly stable, repro-ducible, and sensitive humidity sensor [32] (Figure 3). Thesensitivity of the developed sensor was directly proportionalto the film’s thickness. The best linearity was obtained witha SBA-15 film of 20 nm thickness having the sensitivity of12.32 Hz/RH%.

The sensing of silver ions in aqueous media was demon-strated by the deposition of nanotubular PANI film on QCM,


where the increased mass due to the reduction of silver ionswith PANI caused the decrease in QCM frequency [33]. Theprocedure can be used for monitoring industrial waste watersand searching new resources of silver.

Eight QCM sensor arrays, with five gas chromatographicstationary phases (OV-17, OV-275, PEG, Span 80, andVaseline) as sensing films and PCA method, were usedfor differentiating virgin and extravirgin olive oils fromlampante ones [34]. The method is cheap, easy to use, anddoesn’t employ any solvents or pretreatment of the sample.

QCM was employed to accurately determine the con-centration of nanoparticles in a colloidal suspension using asimple procedure based on the drop casting of nanoparticlesuspension in a volatile solvent, which leaves a dry nanopar-ticle residue after solvent evaporation on the QCM surface[35] (Figure 4). There was a linear response for nanoparticleconcentrations up to 1300 μg/mL in the calibration experi-ments done with serial dilutions of Si and Ag nanopowderin methanol, rhodamine B in methanol, and ferrocene incyclohexane. The developed procedure determined the con-centrations of size-selected, octyl-terminated Si nanocrystalsamples with median diameters in the range of 1.1–14.8 nm.

3. Detection of Biomolecules

A displacement assay was developed for the nonenzy-matic glucose detection, where glucose molecules displaceconcanavalin A (conA) molecules bound to the dextran-functionalized graphene-coated QCM, thereby, leading toa change in frequency [36] (Figure 5). Phenoxy-deriveddextran (DexP) molecules were initially bound to graphene-coated QCM surface by Π-Π stacking, which was followedby the binding of conA molecules based on their specificinteractions with DexP. The dynamic range of the glucosesensing assay was 0.01–7.5 mM with a LOD of 5 μM.

MIP-coated QCM sensor was developed for the deter-mination of albumin concentration [37]. Albumin wasimprinted with 3-dimethylaminopropyl methacrylamide-acrylate. The albumin MIP was then coated on QCM Au elec-trode. In the tetraethylene glycol dimethacrylate-crosslinkedpolymer system, the adsorption capacity of different Au elec-trodes was in the decreasing order of Au-OH > Au-COOH >Au-NH2 > Au, whereas the time taken to achieve a steady-state frequency was in the decreasing order of Au-NH2 < Au-OH < Au-COOH < Au. However, in the trimethylolpropanetrimethacrylate cross-linking system, the adsorption capacityof different electrodes was in the decreasing order of Au >Au-NH2 > Au-OH > Au-COOH. The developed albuminMIP-QCM sensor had higher response to albumin thannon-MIP-QCM sensor. The adsorption ratios of cytochromec : lysozyme : albumin : myoglobin were 160 : 1 : 1942 : 30 and13 : 1 : 249 : 86 for albumin MIP-QCM and non-MIP-QCM,respectively. The developed sensor had a linear range from 60to 150 ppm for albumin. The clinical application of the devel-oped sensor was tested by determining the albumin concen-tration in human serum. The values obtained by MIP-QCMand clinical assay were 4.80 g/dL and 4.60 g/dL, respectively,which showed good correlation and, thereby, demonstratethe potential of the developed sensor for clinical applications.

(a)

(b)

Figure 4: Quartz crystal images: (a) following the application ofa nanocrystal colloidal suspension, circle indicates residual solvent;(b) following complete solvent evaporation (Reipa et al., 2010) [35].(Reprinted with permission from ACS Publications.).

Antibody-bound QCM with Au nanoparticle-based sig-nal amplification was employed for detecting prostate-speci-fic antigen (PSA) and PSA-alpha 1-antichymotrypsin (ACT)complex in human serum (75%) [38]. The LOD of PSA andPSA-ACT complex in 75% human serum was 0.29 ng/mLwith the linear dynamic range of up to 150 ng/mL. The inter-fering signal in human serum was reduced by 98%, whenPBS buffer, having 200 μg/mL BSA, 0.5 M NaCl, 500 μg/mLdextran, and 0.5% Tween 20, was used.

An indirect competitive-QCM immunosensors weredeveloped, where 2 mg/mL of C-reactive protein (CRP) wasbound to the surface, and the change in frequency wasmonitored after providing 200 μL of biotinylated antirat CRPantibody mixed with streptavidin-coated gold nanoparticle[39] (Figure 6). There was 53% signal enhancement by thisprocedure in comparison to the conventional procedureusing unmodified antibody.

QCM immunosensor was developed for the detection ofepidermal growth factor receptor (EGFR) with a linear rangeof 0.01–10 μg/mL [40]. Anti-EGFR antibody was immobi-lized on the gold surface by thiosalicylic acid-based self-assembled monolayer (SAM) followed by activation with1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydroc-hloride (EDC) and N-hydroxysuccinimide (NHS). Two


+

HO

n

nn

n

Dextran

O

O

O

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OO

O

OO

O

O

O

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OH

OH

OH

OH

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O

O

O

O

O

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OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

OH

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OH

OH

OH

OH

1,2-epoxy-3-phenoxypropane

NaOH

40◦C

Dextran derivative

Graphene ConA

Glucose

Glucose

Glucose

QCM Δ f = fn

fn

− f0

f0

+

m

mm

mm

HO

HO

HO

(a)

Measurement setup

(b)

Figure 5: (a) Fabrication process and measurement principle of the displacement-based QCM glucose sensor and (b) the QCMmeasurement setup (Tang et al., 2011) [36]. (Reprinted with permission from Elsevier B.V.)

different immobilization strategies were employed, wherethe protein G-based site-specific immobilization strategywas found to be better than the chemical cross-linking-based strategy as it controlled the orientation and quantityof anti-EGFR-bound to the gold surface. The anti-EGFRcoated QCM surface was effectively regenerated four timesby treatment with 0.1 M NaOH for multiple biosensing runs.The dip-and-dry method was found to be more sensitivethan the real-time flow cell analysis.

Enantioselective MIP-coated QCM was used for thehighly sensitive and selective detection of L tryptophan withLOD of 8.8 μM [41]. MIP was synthesized using acrylamide(AM) as a monomer and trimethylolpropane trimethacrylate(TRIM) as a cross-linking agent. The QCM was then coatedwith thin permeable film coatings of MIP and the enan-tioselectivity was demonstrated by the selective detection ofL-tryptophan with respect to D-tryptophan in citric acidbuffer solutions. The signal obtained by the binding of L-tryptophan was 3-4 fold higher than that obtained from D-tryptophan with the enantiomeric selectivity coefficient of6.4. The effect of cross-linking agent concentration on thesensitivity and specificity of MIP film was also analysed. MIP,

having TRIM/AM molar ratio of 2.21 as the cross-linkingmonomer concentration, showed the highest sensitivity andenantioselectivity for L tryptophan out of the four differentMIPs synthesized.

QCM with dissipation monitoring (QCM-D) was usedfor studying the biospecific glycoprotein-lectin interactions,where four lectins were covalently bound to the thiol-modified Au electrodes of QCM [42]. The frequency anddissipation shifts provided information about the analyticalconcentration and viscoelastic properties of glycoprotein-lectin complex, respectively. A unique lectin-binding patternwas displayed for each glycoprotein, which can be used asa fingerprint to discriminate between various glycoproteins.The developed lectin-bound QCM biosensor can detectglycoproteins in linear range of 50 μg/ML–1 mg/mL and canbe reused many times for two months without any signalloss after regenerating the lectin-bound surface with 10 mMglycine-HCl, pH 2.5.

QCM was coated with an electropolymerized MIP film ofa bis-terthiophene dendron and employed for the detectionof folic acid with a linear range of 0–100 μM and LOD of15.4 μM (6.8 μg) [43] (Figure 7). The relative cross-selectivity


N H

C

X

O

CH2

CH2

S

N H

C

X

O

CH2

CH 2

S

SA-coatedgold colloid

Biotinylated

anti-CRP antibody

++

CRP (coating antigen)

Gold electrode

PZ crystal

Figure 6: Schematic representation of the signal augmentation over QCM surface by the addition of gold colloid in the IC CRP measurementof this study. X is the residue remaining after antibody immobilization and represents the structure of –CO–NH–(CH2)5– (Kim et al., 2010)[39]. (Reprinted with permission from Elsevier B.V.)

of developed QCM sensor for various structurally similarmolecules was in the decreasing order of pteroic acid (50%)> caffeine (40%) > theophylline (6%).

4. Detection of Bacteria

QCM-based immunosensor was developed for the detectionof shrimp pathogenic bacteria, Vibrio harveyi, by the covalentbinding of monoclonal antibody against V. harveyi onto theAu electrode of 5 MHz QCM [44] (Figure 8). The three-step antibody immobilization procedure was followed, whichsequentially involved the formation of SAM of carboxyl-terminated alkanethiol, that is, 3-mercaptopropionic acid,activation of carboxyl groups by N-hydroxysuccinimide(NHS) and 1-ethyl-3-(3-dimethylaminopropyl) carbodi-imide (EDC), and covalent binding of antibody by theiramino groups through EDC-NHS heterobifunctional cross-linking. The developed sensor detected 103–107 CFU/mLof V. harveyi without any cross-reactivity to V. vulnificusand V. parahaemolyticus. The bacterial binding efficientlywas improved by blocking with 1% bovine serum albuminand by optimizing the monoclonal antibody immobilizationdensity.

QCM-based robust and reproducible procedure wasdeveloped for the recognition and discrimination of severalCampylobacter jejuni strains by measuring the dissipationshifts of various bacterial strains, when they are bound tothe lectins immobilized on the gold-coated QCM surface[45]. The developed procedure would be very useful for the

strain discrimination of other bacterial species, especiallypathogenic strains that can be bound to lectins.

QCM-based biosensor was developed for the detec-tion of sulphate-reducing bacterium, D. desulfotomaculumwith a linear range of 1.8 × 104–1.8 × 107 cfu/mL [46].Vancomycin-functionalized magnetic nanoparticles underan external magnetic field formed conjugates with bacteriaafter 30 min incubation and got attached to the surface ofAu electrode. There was no response to vancomycin-resistantbacterium, Vibrio anguillarum.

5. Conclusions and Future Trends

Although QCMs were employed initially in applied physicsto study metals in vacuum, it has progressed subsequentlyto multiple scientific disciplines, such as chemistry, biology,material science, medicine, and environmental monitoring,with increasing complexity of metal interfaces. The QCM-based sensing procedure is simple, cost effective, nonhaz-ardous, real time, and less time, and labour consuming incomparison to conventional assay procedures. Researchershave also demonstrated recently the construction of simulta-neous surface-plasmon resonance (SPR) and QCM-sensingplatform [49], which would lead to next generation ofsensing devices capable of providing lot of useful informa-tion for the advancement of analytical sciences. Q-Sensehas also developed a new technology called quartz crystalmicrobalance with dissipation (QCM-D), which enablesreal-time, label-free measurements of molecular adsorption


S

S

S

O

OH

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S

S

2

N

NN

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H

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O O

=

=

Bis-terthiophene dendron, G1 3IOH (monomer)

Polythiophene(receptor or binding ligand)

Folic acid(template)

QCM sensor

Washing oftemplate

Rebinding oftemplate

Imprinted polymer

Pt electrodeAg/AgCl

electrode

in situ EC-QCM

MIP fabrication

E-MIP film components

n∗

∗

Figure 7: Schematic illustration of the fabrication of a polythiophene-based QCM sensor for folic acid (Apodaca et al., 2011) [43].(Reprinted with permission from ACS Publications.)

S

N

O

O

S N

O

S

NH

S

S

S

S

S

S

S

S

S

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CO

NHCO

NHCO NHCO

NHCO

OH

OH

OH

COO

COO

(1) (2)

(3)

MPA + ME

%MPA is varied in arange of 20–100%

(MAb)

Vibrio harveyi

NHS/EDC

NH2

Au

Au Au Au

Au

COOH

OH

COOH

Figure 8: Schematic diagram showing the procedure for the preparation of monoclonal antibody-functionalized QCM-basedimmunosensor for Vibrio harveyi (Buchatip et al., 2010) [44]. (Reprinted with permission from Elsevier B.V.)


and/or interactions on various surfaces. The dissipationparameter (D) provides novel insights regarding structural(viscoelastic) properties of adsorbed layer. A device based onthe simultaneous QCM and electrochemical measurementswould also be very useful for providing lot of analyticalinformation. However, electrochemical QCM (EQCM) hasa potential limitation as it can only be used for studyingelectroplated, evaporated, or sputtered materials.

QCM-based sensing concept is mature enough and hasbeen demonstrated for a wide range of analytes, but therobust technology comparison with several commerciallyavailable technologies still needs to be critically evaluatedto demonstrate its pros and cons with respect to theexisting technologies. Presently, there are so many advancedanalytical techniques such as SPR-based BIAcore instrumentsfrom GE Healthcare, which offer tremendous advantagesand are being used on a very large scale in industries,academia, and healthcare. In addition, there are microtiterplate immunoassays such as enzyme-linked immunosorbentassays, fluorescent immunoassays, and chemiluminescentimmunoassays, which have very high sensitivity and highthroughput and are still used widely as the gold standardfor disease diagnostics. However, QCM may find a particularniche in certain sensing applications based on the technol-ogy advancement in the near future. It has already beendemonstrated recently that the development of a combinedsystem, such as QCM and SPR or QCM and electrochemicalmeasurement system, would be immensely useful as it wouldprovide lot of additionally useful information in comparisonto an individual analytical technique.

References

[1] J. Curie and P. Curie, “An oscillating quartz crystal massdetector,” Rendu, vol. 91, pp. 294–297, 1880.

[2] G. Z. Sauerbrey, “Use of quartz vibration for weighing thinfilms on a microbalance,” Physik Journal, vol. 155, pp. 206–212, 1959.

[3] H. H. Lu, Y. K. Rao, T. Z. Wu, and Y. M. Tzeng, “Direct char-acterization and quantification of volatile organic compoundsby piezoelectric module chips sensor,” Sensors and Actuators B,vol. 137, no. 2, pp. 741–746, 2009.

[4] M. M. Ayad and N. L. Torad, “Alcohol vapours sensor basedon thin polyaniline salt film and quartz crystal microbalance,”Talanta, vol. 78, no. 4-5, pp. 1280–1285, 2009.

[5] A. Bello, F. Bianchi, M. Careri et al., “Potentialities of amodified QCM sensor for the detection of analytes interactingvia H-bonding and application to the determination ofethanol in bread,” Sensors and Actuators B, vol. 125, no. 1, pp.321–325, 2007.

[6] M. Kikuchi and S. Shiratori, “Quartz crystal microbalance(QCM) sensor for CH3SH gas by using polyelectrolyte-coatedsol-gel film,” Sensors and Actuators B, vol. 108, no. 1-2, pp.564–571, 2005.

[7] Z. Ying, Y. Jiang, X. Du, G. Xie, J. Yu, and H. Tai, “Polymercoated sensor array based on quartz crystal microbalance forchemical agent analysis,” European Polymer Journal, vol. 44,no. 4, pp. 1157–1164, 2008.

[8] Z. Ying, Y. Jiang, X. Du, G. Xie, J. Yu, and H. Wang, “PVDFcoated quartz crystal microbalance sensor for DMMP vapor

detection,” Sensors and Actuators B, vol. 125, no. 1, pp. 167–172, 2007.

[9] I. A. Koshets, Z. I. Kazantseva, Y. M. Shirshov, S. A. Cherenok,and V. I. Kalchenko, “Calixarene films as sensitive coatings forQCM-based gas sensors,” Sensors and Actuators B, vol. 106, no.1, pp. 177–181, 2005.

[10] M. Matsuguchi and T. Uno, “Molecular imprinting strategyfor solvent molecules and its application for QCM-based VOCvapor sensing,” Sensors and Actuators B, vol. 113, no. 1, pp. 94–99, 2006.

[11] J. Rabe, S. Buttgenbach, J. Schroder, and P. Hauptmann,“Monolithic miniaturized quartz microbalance array and itsapplication to chemical sensor systems for liquids,” IEEESensors Journal, vol. 3, no. 4, pp. 361–368, 2003.

[12] F. L. Dickert, O. Hayden, and M. E. Zenkel, “Detection ofvolatile compounds with mass-sensitive sensor arrays in thepresence of variable ambient humidity,” Analytical Chemistry,vol. 71, no. 7, pp. 1338–1341, 1999.

[13] B. Wyszynski, P. Somboon, and T. Nakamoto, “ChemisorbedPEGylated lipopolymers as sensing film supports for QCModor sensors,” Sensors and Actuators B, vol. 130, no. 2, pp. 857–863, 2008.

[14] J. W. Park, S. Kurosawa, H. Aizawa, Y. Goda, M. Takai, andK. Ishihara, “Piezoelectric immunosensor for bisphenol Abased on signal enhancing step with 2-methacrolyloxyethylphosphorylcholine polymeric nanoparticle,” Analyst, vol. 131,no. 1, pp. 155–162, 2006.

[15] J. W. Park, S. Kurosawa, H. Aizawa et al., “Dioxin immunosen-sor using anti-2,3,7,8-TCDD antibody which was producedwith mono 6-(2,3,6,7-tetrachloroxanthene-9-ylidene) hexylsuccinate as a hapten,” Biosensors and Bioelectronics, vol. 22,no. 3, pp. 409–414, 2006.

[16] H. Zeng, Y. Jiang, G. Xie, and J. Yu, “Polymer coated QCMsensor with modified electrode for the detection of DDVP,”Sensors and Actuators B, vol. 122, no. 1, pp. 1–6, 2007.

[17] Y. K. Yuan, X. L. Xiao, Y. S. Wang et al., “Quartz crystalmicrobalance with β-cyclodextrin/TiO2 composite films cou-pled with chemometrics for the simultaneous determinationof urinary 1- and 2-naphthol,” Sensors and Actuators B, vol.145, no. 1, pp. 348–354, 2010.

[18] M. Matsuguchi, Y. Kadowaki, K. Noda, and R. Naganawa,“HCl gas monitoring based on a QCM using morpholine-functional styrene-co-chloromethylstyrene copolymer coat-ings,” Sensors and Actuators B, vol. 120, no. 2, pp. 462–466,2007.

[19] M. Matsuguchi and Y. Kadowaki, “Poly(acrylamide) deriva-tives for QCM-based HCl gas sensor applications,” Sensors andActuators B, vol. 130, no. 2, pp. 842–847, 2008.

[20] P. Sun, Y. Jiang, G. Xie, X. Du, and J. Hu, “A room temperaturesupramolecular-based quartz crystal microbalance (QCM)methane gas sensor,” Sensors and Actuators B, vol. 141, no. 1,pp. 104–108, 2009.

[21] G. Xie, P. Sun, X. Yan, X. Du, and Y. Jiang, “Fabrication ofmethane gas sensor by layer-by-layer self-assembly of polyani-line/PdO ultra thin films on quartz crystal microbalance,”Sensors and Actuators B, vol. 145, no. 1, pp. 373–377, 2010.

[22] A. Palaniappan, S. Moochhala, F. E. H. Tay, X. Su, and N.C. L. Phua, “Phthalocyanine/silica hybrid films on QCM forenhanced nitric oxide sensing,” Sensors and Actuators B, vol.129, no. 1, pp. 184–187, 2008.

[23] M. Matsuguchi, Y. Kadowaki, and M. Tanaka, “A QCM-basedNO2 gas detector using morpholine-functional cross-linkedcopolymer coatings,” Sensors and Actuators B, vol. 108, no. 1-2,pp. 572–575, 2005.


[24] F. L. Dickert, A. Haunschild, V. Kuschow, M. Reif, andH. Stathopulos, “Mass-sensitive detection of solvent vapors.Mechanistic studies on host-guest sensor principles by FT-IR spectroscopy and BET adsorption analysis,” AnalyticalChemistry, vol. 68, no. 6, pp. 1058–1061, 1996.

[25] B. Ding, J. Kim, Y. Miyazaki, and S. Shiratori, “Electrospunnanofibrous membranes coated quartz crystal microbalance asgas sensor for NH3 detection,” Sensors and Actuators B, vol.101, no. 3, pp. 373–380, 2004.

[26] N. Van Quy, V. A. Minh, N. Van Luan, V. N. Hung, and N. VanHieu, “Gas sensing properties at room temperature of a quartzcrystal microbalance coated with ZnO nanorods,” Sensors andActuators B, vol. 153, pp. 188–93, 2011.

[27] S. W. Lee, N. Takahara, S. Korposh, D. H. Yang, K. Toko,and T. Kunltake, “Nanoassembled thin film gas sensors. III.sensitive detection of amine odors using TiO2/ poly(acrylicacid) ultrathin film quartz crystal microbalance sensors,”Analytical Chemistry, vol. 82, no. 6, pp. 2228–2236, 2010.

[28] C. Zhang, X. Wang, J. Lin, B. Ding, J. Yu, and N. Pan,“Nanoporous polystyrene fibers functionalized by polyethy-leneimine for enhanced formaldehyde sensing,” Sensors andActuators B, vol. 152, pp. 316–323, 2011.

[29] H. S. Guo, J. M. Kim, S. M. Chang, and W. S. Kim, “Chiralrecognition of mandelic acid by l-phenylalanine-modifiedsensor using quartz crystal microbalance,” Biosensors andBioelectronics, vol. 24, no. 9, pp. 2931–2934, 2009.

[30] S. Munoz-Aguirre, A. Yoshino, T. Nakamoto, and T. Mori-izumi, “Odor approximation of fruit flavors using a QCModor sensing system,” Sensors and Actuators B, vol. 123, no.2, pp. 1101–1106, 2007.

[31] A. Ozmen, F. Fekce, M. A. Ebeoglu, C. Tasaltin, and Z.Z. Ozturk, “Finding the composition of gas mixtures by aphthalocyanine-coated QCM sensor array and an artificialneural network,” Sensors and Actuators B, vol. 115, pp. 450–454, 2006.

[32] Y. Zhu, H. Yuan, J. Xu, P. Xu, and Q. Pan, “Highly stable andsensitive humidity sensors based on quartz crystal microbal-ance coated with hexagonal lamelliform monodisperse meso-porous silica SBA-15 thin film,” Sensors and Actuators B, vol.144, no. 1, pp. 164–169, 2010.

[33] M. M. Ayad, N. Prastomo, A. Matsuda, and J. Stejskal, “Sens-ing of silver ions by nanotubular polyaniline film deposited onquartz-crystal in a microbalance,” Synthetic Metals, vol. 160,no. 1-2, pp. 42–46, 2010.

[34] M. E. Escuderos, S. Sanchez, and A. Jimenez, “Quartz CrystalMicrobalance (QCM) sensor arrays selection for olive oilsensory evaluation,” Food Chemistry, vol. 124, no. 3, pp. 857–862, 2011.

[35] V. Reipa, G. Purdum, and J. Choi, “Measurement of nanopar-ticle concentration using quartz crystal microgravimetry,”Journal of Physical Chemistry B, vol. 114, no. 49, pp. 16112–16117, 2010.

[36] D. Tang, Q. Li, J. Tang, B. Su, and G. Chen, “An enzyme-free quartz crystal microbalance biosensor for sensitive glu-cose detection in biological fluids based on glucose/dextrandisplacement approach,” Analytica Chimica Acta, vol. 686, pp.144–149, 2011.

[37] T. Y. Lin, C. H. Hu, and T. C. Chou, “Determination ofalbumin concentration by MIP-QCM sensor,” Biosensors andBioelectronics, vol. 20, no. 1, pp. 75–81, 2004.

[38] Y. Uludag and I. E. Tothill, “Development of a sensitive detec-tion method of cancer biomarkers in human serum (75%)using a quartz crystal microbalance sensor and nanoparticles

amplification system,” Talanta, vol. 82, no. 1, pp. 277–282,2010.

[39] N. Kim, D. K. Kim, and Y. J. Cho, “Gold nanoparticle-based signal augmentation of quartz crystal microbal-ance immunosensor measuring C-reactive protein,” CurrentApplied Physics, vol. 10, no. 4, pp. 1227–1230, 2010.

[40] J. C. Chen, S. Sadhasivam, and F. H. Lin, “Label freegravimetric detection of epidermal growth factor receptorby antibody immobilization on quartz crystal microbalance,”Process Biochemistry, vol. 46, no. 2, pp. 543–550, 2011.

[41] F. Liu, X. Liu, S. C. Ng, and H. S. O. Chan, “Enantioselectivemolecular imprinting polymer coated QCM for the recogni-tion of l-tryptophan,” Sensors and Actuators B, vol. 113, no. 1,pp. 234–240, 2006.

[42] M. E. Yakovleva, G. R. Safina, and B. Danielsson, “A study ofglycoprotein-lectin interactions using quartz crystal microbal-ance,” Analytica Chimica Acta, vol. 668, no. 1, pp. 80–85, 2010.

[43] D. C. Apodaca, R. B. Pernites, R. R. Ponnapati, F. R. DelMundo, and R. C. Advincula, “Electropolymerized molecu-larly imprinted polymer films of a bis-terthiophene dendron:folic acid quartz crystal microbalance sensing,” ACS AppliedMaterials & Interfaces, vol. 3, pp. 191–203, 2011.

[44] S. Buchatip, C. Ananthanawat, P. Sithigorngul, P. Sangvanich,S. Rengpipat, and V. P. Hoven, “Detection of the shrimppathogenic bacteria, Vibrio harveyi, by a quartz crystalmicrobalance-specific antibody based sensor,” Sensors andActuators B, vol. 145, no. 1, pp. 259–264, 2010.

[45] M. E. Yakovleva, A. P. Moran, G. R. Safina, T. Wadstrom, andB. Danielsson, “Lectin typing of Campylobacter jejuni usinga novel quartz crystal microbalance technique,” AnalyticaChimica Acta, vol. 694, no. 1-2, pp. 1–5, 2011.

[46] Y. Wan, D. Zhang, and B. Hou, “Determination of sulphate-reducing bacteria based on vancomycin-functionalized mag-netic nanoparticles using a modification-free quartz crystalmicrobalance,” Biosensors & Bioelectronics, vol. 25, no. 7, pp.1847–1850, 2010.

[47] N. Tsuru, M. Kikuchi, H. Kawaguchi, and S. Shiratori, “Aquartz crystal microbalance sensor coated with MIP for“Bisphenol A” and its properties,” Thin Solid Films, vol. 499,no. 1-2, pp. 380–385, 2006.

[48] S. Kurosawa, H. Aizawa, and J. W. Park, “Quartz crystalmicrobalance immunosensor for highly sensitive 2,3,7,8-tetrachlorodibenzo-p-dioxin detection in fly ash from munic-ipal solid waste incinerators,” Analyst, vol. 130, no. 11, pp.1495–1501, 2005.

[49] J. Kim, S. Kim, T. Ohashi, H. Muramatsu, S. M. Chang, and W.S. Kim, “Construction of simultaneous SPR and QCM sensingplatform,” Bioprocess and Biosystems Engineering, vol. 33, no. 1,pp. 39–45, 2010.

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